Issue 3, 2016

Chemo- and regioselective oxygenation of C(sp3)–H bonds in aliphatic alcohols using a covalently bound directing activator and atmospheric oxygen

Abstract

Chemically reactive directing groups (directing activators) represent a promising strategy for mild and regioselective C(sp3)–H functionalization. The use of a radical N-oxyl directing activator promoted the aerobic oxygenation of benzylic, propargylic, tertiary, and unactivated acyclic methylene C(sp3)–H bonds in aliphatic alcohols with γ- (or δ-) selectivity under mild conditions (room temperature to 50 °C). The reaction was unaffected by the presence of various oxidation-sensitive functional groups, which proved to be problematic in previously reported studies on the oxidation of C(sp3)–H bonds. Structural modifications on the directing activator altered the regioselectivity, and thus provided an ultra-remote aerobic C(sp3)–H oxygenation. The observed reactivity and regioselectivity could be rationalized in terms of the intramolecular conformational accessibility of the N-oxyl radical and the electronic characteristics of C(sp3)–H bonds.

Graphical abstract: Chemo- and regioselective oxygenation of C(sp3)–H bonds in aliphatic alcohols using a covalently bound directing activator and atmospheric oxygen

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Nov 2015
Accepted
26 Nov 2015
First published
27 Nov 2015
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2016,7, 1904-1909

Chemo- and regioselective oxygenation of C(sp3)–H bonds in aliphatic alcohols using a covalently bound directing activator and atmospheric oxygen

J. Ozawa, M. Tashiro, J. Ni, K. Oisaki and M. Kanai, Chem. Sci., 2016, 7, 1904 DOI: 10.1039/C5SC04476F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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